JP4450630B2 - Rhodium complex, iridium complex, production method thereof, and electronic component using the same - Google Patents

Description

  The present invention relates to an organometallic compound that can be used as a phosphorescent emitter.

Organometallic compounds, particularly d ⁸ metal compound, as active components (functional materials) in the near future, it will find use as functional components in applications where many different. It can be regarded as belonging to the electronics industry in the broadest sense.

  Electroluminescent devices based on organic components (for the general description of structures see Patent Document 1 and Patent Document 2), as well as their individual components, ie organic light emitting diodes (OLEDs), have already been introduced to the market. It is shown by a commercial car radio with an “organic display” from a company called Pioneer. Further such products will be introduced shortly. Nonetheless, these displays have turned into true competitors to liquid crystal displays (LCDs) that currently dominate the market, and much further improvement is needed here to outperform the latter.

  The development in this respect that has appeared in the last two years is the use of organometallic compound complexes that exhibit phosphorescence instead of fluorescence (Non-Patent Document 1).

  For theoretical spin statistical reasons, the use of organometallic compounds as phosphorescent emitters allows up to four times the energy and power efficiency. Whether this new development is established will depend largely on finding a suitable device configuration that can make these advantages effective in OLEDs (triple emission = singlet emission comparable to fluorescence = phosphorescence). Dependent. As important conditions for practical applications, it can now be mentioned in particular the long activity life, the high stability to temperature and the low duty-operating voltage in order to enable mobile use.

  In addition, there must be effective chemical access to the corresponding organometallic compound. Organic rhodium and iridium compounds are particularly important. In the latter case, especially in view of the rhodium and iridium prices, it is of crucial importance that effective access to the corresponding derivatives is possible.

So far, two types of OLED designs with phosphorescent emitters as chromophore components have been described in the literature. The first type (type 1) typically has the following layered structure (Non-Patent Document 2):
Carrier plate = substrate (usually glass or plastic film).
Transparent anode (usually indium tin oxide (ITO)).
Hole transport layer: usually based on triarylamine derivatives.
Electron transport / light emitting layer: This layer consists of an electron transport material doped with a phosphorescent emitter.
Electron transport layer: Usually based on aluminum-tris-8-hydroxy-quinoxalinate (AIQ ₃ ).
Cathode: Here, metals, metal combinations or metal alloys with a low output function, such as Al-Li, are used.

The second type (type 2) typically has the following layered structure (Non-Patent Document 3):
1. Carrier plate = substrate (usually glass or plastic film).
2. A transparent anode (usually indium tin oxide (ITO)).
3. Hole transport layer: usually based on triarylamine derivatives.
4). Matrix radiation layer: This layer usually consists of a matrix material based on a triarylamine derivative, which is doped with a phosphorescent emitter.
5). Electron transport / hole barrier layer: usually based on nitrogen heterocyclene.
6). Electron transport layer: usually based on aluminum-tris-8-hydroxy-quinoxalinate (AIQ ₃ ).
7). Cathode: In principle, a metal, a combination of metals or a metal alloy with a low output function, such as for example Al, is used here.

It is also possible to separate light from a thin transparent cathode. Because the lifetime of these devices is generally greatly reduced in the presence of water and oxygen, such devices are made in a corresponding structure (depending on the application), contacted, and finally also sealed. .
U.S. Pat. No. 4,539,507 U.S. Pat. No. 5,151,629 M.M. A. Bardo, S. Ramansky, P.A. E. Burroughs, M.C. E. Thompson, S.H. R. Forest, Applied Physics Letters, 1999, 75, 4-6 M.M. E. Thompson et al., Proceedings of SPIE, July 31-August 2, 2000, San Diego, USA, 4105, 119-124 T. T. Tsutsui et al., Japanese Journal of Applied Physics, 1999, Vol. 38, L1502-L1504

  The OLED characterization data described above reveals two weaknesses: On the other hand, emitters based on tris-ortho metallized iridium complexes as described above are effective in creating effective blue, especially deep blue OLEDs. Is not suitable. This is because known phosphorescent emitters do not emit light in deep blue, i.e. at an emission frequency λmax of less than 465 nm. However, deep blue phosphorescent emitters are critically important, especially for the production of full color displays (for which the red-green-blue primaries are used).

  On the other hand, it is clear from the efficiency-luminosity curve that the efficiency decreases significantly with increasing luminous intensity. This means that the high luminosity actually required is achieved only through high power inputs. However, large power inputs require large battery power of portable devices (cell phones, laptops, etc.). In addition, large power inputs are largely converted to heat, leading to thermal damage to the display.

  The following problems arise from the shortcomings in the prior art. On the one hand, for example, blue-especially deep blue-triple emitters need to be made, while on the other hand triple-wire emitters that exhibit efficiency-luminosity curves that are as straight as possible even in the presence of high luminosity are available. Must be.

5'-mono-, 5 ', 5 "-di- and 5', 5", 5 "'-tris-cyano grouped-tris-ortho metallized-organic rhodium and organic iridium compounds- consisting of formula (I) compound / formula (Ia) a compound, formula (II) comprises a compound / formula (IIa) consists of compounds formula (III) a compound / formula consisting (IIIa) compounds or consisting formula (IV) compound / With compounds of formula (IVa) —which are the subject of the present invention—is a centrally important component for the production of highly efficient triple-wire emitters. Depending on important material properties such as the wavelength of the phosphorescence emission, ie emitter color, phosphorescence quantum yield, redox and temperature (to name a few examples). Degree stability can be adjusted.

5'-mono-, 5 ', 5 "-di- and 5', 5", 5 "'-tris-cyano grouped-tris-ortho metallated-organometallic rhodium and organometallic iridium compounds-chemical formula (I) Compound / compound of formula (Ia), compound of formula (II) / compound of formula (IIa), compound of formula (III) / compound of formula (IIIa) or compound of formula (IV) -By compounds consisting of (IVa) has been novel and has not been described in publications until now, but their efficient preparation and utilization as pure materials has led to many electro-optical applications Very important.

  Surprisingly, the wavelength of the phosphorescence emission of the triplet emitter, ie the “color” of the emitted light, undergoes a light color shift due to the introduction of cyano groups at the 5′-, 5 ″-and 5 ″ ′-sites (see below). (See Table 1).

5'-mono-, 5 ', 5 "-di-, and 5', 5", 5 "'-tri-cyano grouped-tris-ortho metallated-organic rhodium and organic iridium compounds (in the gist of the present invention) A compound of formula (I) / a compound of formula (Ia), a compound of formula (II) / a compound of formula (IIa), a compound of formula (III) / a compound of formula (IIIa), or Apart from its direct use in light-emitting devices of formula (IV) / by formula (IVa), said compound can convert a cyano group into a number of groups by current methods described in the literature. It is also a centrally important building material for efficient triple-line emitter production in publications, proceeding from known structures, the methods known in publications include alcohol, alcohol As well as heterocycles such as azolenes, diazolenes, triazolenes, oxazolinenes, oxazolenes, oxadiazolenes, thiazolenes, thiodiazolenes, and their benzene condensed derivatives. It also opens the way to Clen.

  5'-mono-, 5 ', 5 "-di- and 5', 5", 5 "'-tricyano-trisortho metallization, organometallic rhodium and organometallic iridium compounds, and methods for their preparation are novel This has not been previously described in the publication, and applies in particular to the cyanation of halogenated aromatic ligands attached to the metal center, ie the cyanation of metal complexes by substitution of halogen groups by cyano groups. The efficient preparation and availability of these cyanide compounds as pure materials is very important for various electro-optic applications.

  Surprisingly, 5'-mono-, 5 ', 5 "-di- and 5', 5", 5 '"-trihalogen substitution-tris ortho-metallated organorhodiums of formula (V) and formula (VI) [Preparation according to the unpublished German Patent No. 101099027.7], i.e. consisting of formula (I) / formula (Ia), consisting of formula (II) / formula (IIa) A new cyano grouped organometallic compound of the formula (III) / Chemical Formula (IIIa) or starting from an organometallic aryl halide of the formula (IV) / Chemical Formula (IVa) —in accordance with Schemes 1 and 2—optionally In the presence of transition metals, transition metal compounds and phosphorus-containing additives, and as reaction temperature, reaction medium, concentration and reaction time About 90-98% yield without a chromatographic purification step by a stoichiometric conversion reaction with a transition metal cyanide or by a catalytic conversion reaction with a transition metal cyanide with appropriate selection of the appropriate reaction parameters. Optionally after recrystallization, reproducible with> 99% purity according to NMR and HPLC (see Examples 1-6).

The method described above is particularly characterized by three characteristics:
First, selective 5′-mono-, 5 ′, 5 ″ -di- and 5 ′, 5 ″, 5 ″ ′-tri of conjugated aryl halides, ie, organometallic aryl halides. -Cyano grouping is unexpected and unknown in this form.
Secondly, the high conversion achieved, which is reflected in the very good reproduction of the isolated product, is surprising for cyanide coupling of conjugated aryl halides. , Specific.
Thirdly, the compound obtained is produced without expensive chromatographic purification, optionally after crystallization, with a very good purity of> 99% according to NMR and HPLC. This is essential for use in optoelectronic components, more precisely for use as an intermediate for the preparation of suitable compounds.

  As mentioned above, the compounds according to the invention are novel because they have not been previously described.

Therefore, the compound according to scheme 1 consisting of chemical formula (I) and chemical formula (II) is the gist of the present invention.
Scheme 1:

(In the formula, symbols and subscripts have the following meanings:
M Rh, Ir;
Z is N, CR, all the same or different;
YO, S, Se;
R 1 is H, F, Cl, NO ₂ , CN, a linear or branched or cyclic alkyl group or alkoxyl group having 1 to 20 carbon atoms, where it is in the alkyl group or alkoxyl group One or more non-neighboring CH ₂ groups can be substituted with —O—, —S—, —NR ¹ —, or —CONR ² —, wherein the alkyl group or alkoxyl group there one or more H atoms may be substituted with an aryl or heteroaryl group, with F or 4 to 14 carbon atoms, and the carbon atoms, one or more non Several substituents R, which can be substituted by an aromatic group R, can be further monocyclic or polycyclic on the same ring as well as on two different rings combined . an expression system It can be formed;
R ¹ and R ² are the same or different and are H or an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms;
n is 1, 2 or 3. )

A further form of embodiment of the present invention is by means of their Rh and Ir complexes having simultaneously a ligand of the type as in the compound of formula (I) and those of the compound of formula (II), ie a mixed ligand system. Indicated. These are described by compounds of formula (Ia) according to scheme 2 and compounds of formula (IIa):
Scheme 2:

( Wherein the symbols and subscripts have the meanings given under chemical formulas (I) and (II)).

According to the invention, a compound of formula (I) , a compound of formula (Ia) , a compound of formula (II) and a compound of formula (IIa) (wherein S applies to the symbol Y = O) Is given priority.

  In addition, according to the present invention, a compound in which the ring bonded to the metal M by a nitrogen donor atom is a pyrazine, pyridazine, pyrimidine or triazine heterocyclic ring is preferable.

A compound of formula (III) and a compound of formula (IV) according to the invention,

Or a further form of embodiments of the invention, i.e. a ligand of the type as in the case of a compound of formula (III) and a ligand of a compound of formula (IV), i.e. a compound and formula of formula (IIIa) Particularly preferred are these rhodium and iridium complexes having simultaneously a mixed ligand system as described for the compound consisting of (IVa).

( Wherein the symbols and subscripts have the meanings described under the compound consisting of chemical formula (I) and the compound consisting of chemical formula (II),
a is 0, 1, 2, 3 or 4;
b is 0, 1, 2 or 3 . )

  A further subject matter of the present invention is a process for preparing a compound comprising the chemical formula (I) and a compound comprising the chemical formula (II) by the conversion reaction of the compound comprising the chemical formula (V) and the compound comprising the chemical formula (VI), respectively.

(Where
X is Cl, Br or I;
M, Z, the group R and the indices a, b and n have the meanings mentioned under the compounds of the chemical formula (I) and the compounds of the chemical formula (II), respectively, together with the cyanating agent. )

The method according to the invention is illustrated by scheme 2:
Scheme 2:

A further subject matter of the present invention consists of the chemical formula (III), respectively, by the conversion reaction of the compound of the chemical formula (VII) and the compound of the chemical formula (VIII) using a cyanating agent as illustrated in Scheme 3. A method for preparing a compound comprising a compound and a chemical formula (IV).
Scheme 3:

The source of the cyanide according to the invention is a compound containing an ionically or coordinately bound cyanide ion, and thus, for example, sodium, potassium, magnesium, tetraethylammonium, tetrabutylammonium, nickel (II), copper (I), silver (I), zinc (II) cyanide, or sodium and potassium dicyano copper (I), tetracyano copper (II), tetracyano zinc (II), tetracyano nickel ( II) acid salt, tetracyanopalladium (II) acid salt.

  Preferred cyanating agents are on the one hand transition metal cyanides such as, for example, copper (I) cyanide or nickel (II) cyanide. These cyanating agents are hereinafter referred to as cyanating agents (1).

  A further preferred cyanating agent is zinc (II) cyanide in the presence of zinc and in the presence of nickel, or palladium, or a compound of nickel or palladium, and optionally a phosphorus-containing additive. These cyanating agents are hereinafter referred to as cyanating agents (2).

The nickel or nickel compounds according to the invention for the cyanating agent (2) are, for example, elemental nickel, sponge nickel, nickel on diatomaceous earth, nickel on aluminum oxide, nickel on silica, nickel on carbon, acetic acid Nickel (II), nickel (II) acetylacetonate, nickel (II) chloride, bromide, iodide, NiL ₂ X ₂ type addition compounds (where X is chlorine, bromine, iodine, And L correspond to neutral ligands such as ammonia, acetonitrile, propionitrile or benzonitrile), nickel (II) nitrate, nickel (II) sulfate, nickel (II) succinate, bis-cycloocta Diene nickel (0).

The palladium or palladium compounds according to the invention for the cyanating agent (2) are, for example, elemental palladium, palladium sponge, palladium black, palladium on activated carbon, palladium on aluminum oxide, palladium on silica, sodium, potassium , Palladium on alkali metal or alkaline earth metal carbonates such as calcium, strontium or barium carbonate, or palladium on strontium or barium sulfate, or eg palladium (II) acetate, palladium trifluoroacetate ( II), palladium (II) propionate, palladium (II) acetylacetonate, palladium (II) chlorides, bromides, iodides and other palladium compounds, addition compounds of the type PdL ₂ X ₂ (where X The chlorine , Bromine and iodine, and L represents a neutral ligand such as ammonia, acetonitrile, propionitrile, benzonitrile or cyclooctadiene), palladium (II) nitrate, palladium sulfate (II ), Tetraminepalladium acetate (II), tetrakis (acetonitrile) -palladium (II) tetrafluoroborate, sodium and potassium tetracyanopalladates, tetrakis (triphenylphosphino) palladium (0), and tris (dibenzylideneacetone) ) -Dipalladium (0).

  According to the invention, phosphine is used as a phosphorus-containing additive in the case of the cyanating agent (2). The phosphine ligands according to the invention for the cyanating agent (2) are tri-arylphosphine, di-aryl-alkyl-phosphine, aryl-dialkyl-phosphine, tri-alkylphosphine, tri-hetaryl-phosphine, di-hetaryl. -Alkyl-phosphine, hetaryldialkyl-phosphine, wherein the substituents on the phosphorus are the same or different and can be chiral or achiral, one of the substituents or More than that, several phosphorous groups of phosphines can be bound, and here some of these bonds can be one or more metal atoms, thus for example tri-phenyl Phosphine, tri-o-tolylphosphine, tri-mesitylphosphine, tri-o- Nisylphosphine, tri- (2,4,6-trismethoxyphenyl) phosphine, t-butyl-di-o-tolylphosphine, di-t-butyl-o-tolylphosphine, dicyclohexyl-2-biphenylphosphine, di-t -Butyl-2-biphenylphosphine, triethylphosphine, triisopropylphosphine, tricyclohexylphosphine, tri-t-butylphosphine, tri-t-pentylphosphine, bis (di-t-butylphosphino) methane, 1,1 ' -Bis (di-t-butylphosphino) ferrocene.

According to the invention, the molar ratio of the cyanating agents (1) and (2) to the compound of the formula (III) and the compound of the formula (IV), respectively, is 1n: 1 to 10n: 1 .

The molar ratio of zinc (II) cyanide to zinc in the cyanating agent (2) according to the invention is 1: 0.1 to 1: 0.001 .

  According to the present invention, the molar ratio of nickel, nickel compound, palladium or palladium compound to the compound of chemical formula (III) and the compound of chemical formula (IV), respectively, is 0.1n: 1 to 0.00001n: 1.

  According to the present invention, the molar ratio of phosphorus-containing additive to nickel, nickel compound, palladium or palladium compound is 0.5: 1 to 1000: 1.

  The reaction medium according to the invention is a dipolar aprotic solvent and is therefore a nitrile such as, for example, acetonitrile, propionitrile or benzonitrile, or an N, N— such as dimethylformamide, dimethylacetamide or N-methylpyrrolidinone. Dialkylamides, sulfoxides such as dimethyl sulfoxide, sulfones such as sulfone dimethyl sulfone or sulfolane.

  According to the invention, the conversion reaction is carried out in the temperature range from 60 ° C. to 200 ° C., preferably from 80 ° C. to 170 ° C., particularly preferably from 100 ° C. to 160 ° C.

  According to the present invention, rhodium-containing and iridium-containing free forms-compounds of formula (III), compounds of formula (IV), compounds of formula (V) and compounds of formula (VI)- It is in the range of 0005 mol / l to 2 mol / l, particularly preferably 0.002 mol / l to 0.1 mol / l.

  According to the invention, the rhodium-containing and iridium-containing free forms can be present dissolved or suspended in the reaction medium.

  According to the invention, the reaction is carried out within a period of 1 hour to 100 hours, preferably within a period of 1 hour to 60 hours.

  According to the invention, the reaction can be carried out with the addition of inert, crushed objects, such as ceramic, glass, or metal balls or Pall rings or Raschig rings. .

  Samples of the compound consisting of the chemical formula (I), the compound consisting of the chemical formula (II), the compound consisting of the chemical formula (III) and the compound consisting of the chemical formula (IV) are prepared, among others, by the synthesis method described here. can do.

  Iridium and rhodium compounds according to the present invention include organic photo diodes (OLEDs), organic integrated circuits (O-ICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic solar cells (O-SCs), organic lasers. It can be used in electronic components such as diodes (O-lasers), organic color filters for liquid crystal displays, or organic photoreceptors. These are also part of the present invention.

The invention is illustrated in more detail in the following examples, but is not intended to be limited thereto. From this description, one skilled in the art can produce further complexes according to the invention and use the process according to the invention without inventive activity.
[Example]

1. Synthesis of symmetrically and asymmetrically functionalized tris-ortho metalation-organic rhodium and organic iridium compounds:
The following syntheses were carried out in a dry solvent under a protective gas atmosphere unless indicated to the contrary. The educt was obtained from Aldrich [sodium cyanide, copper cyanide (I, zinc cyanide (II), zinc, tetrakis (triphenylphosphino) palladium (0), N-methylpyrrolidone (NMP) Fac-tris [2- (2-pyridinyl-κN) (5-bromophenyl) -κC] -iridium (III), fac-tris [2-2-pyridinyl-κN] ((4-fluoro) -5 -Bromophenyl) -κC] -iridium (III), fac-tris [2- (2-pyridinylκN) (4,6-difluoro-5-bromophenyl-κC) iridium (III), and fac-tris [2 -(2-Pyridinyl-κN) (4-methoxy-5-bromophenyl) κC] iridium (III) is described in the unpublished German Patent No. 10109027.7. As it was obtained.

Assignment of the ¹ H-NMR signal was partially confirmed by the H-H-COSY spectrum, and that of the ¹³ C { ¹ H} -NMR spectrum in each case was confirmed by the DEPT-135 spectrum.

Numbering scheme for assignment of ¹ H-NMR signal: [C. Coudre, S. According to Frecy, JP-Roney, Chemical Communications, 1998, pages 663-664]:

Scheme 3:

fac-tris [2- (2-pyridinyl-κN) (5-cyanophenyl) κC] -iridium (III))
Method A: Use of cyanating agent 1 8.915 g (10 mmol) of fac-tris [2- (2-pyridinyl-κN) (5-bromophenyl) κC] iridium (III) and copper cyanide in 150 ml of NMP (L) A suspension of 5.374 g (60 mmol) was heated at 145 ° C. for 60 hours. After cooling, the brown solution was poured at once into a 50 ° C. hot solution containing 7.4 g of sodium in a mixture of 500 ml of water and 500 ml of ethanol and stirred at 50 ° C. for 2 hours. Subsequently, the microcrystalline precipitate was collected by filtration (P4). The microcrystalline yellow precipitate was mixed three times, each time with 100 ml of a solution of 7.4 g sodium cyanide in a mixture of 500 ml water and 500 ml ethanol, each time three times with a mixture of ethanol and water. The solution was washed with 100 ml of liquid (1: 1, volume) twice more with 100 ml of ethanol, and then dried under vacuum (60 ° C., 10 ⁻⁴ mbar). The yield was 7.094-7.236 g corresponding to 97.2-99.1% with a purity of> 99.0% according to ¹ H-NMR.

Method B: Use of Cyanating Agent 2 In 150 ml of NMP, 8.915 g (10 mmol) of fac-tris [2- (2-pyridinyl-κN) (5-bromophenyl) -κC] -iridium (III), zinc cyanide (II) A suspension containing 4.403 g (37.5 mmol) and zinc powder 98 mg (1.5 mmol) was mixed with 347 mg (0.3 mmol) and heated at 100 ° C. for 60 hours. Preparation similar to method A. The yield was 6.877-6.956 g, corresponding to 94.2-95.3%, with a purity of> 99.0% according to ¹ H-NMR.
¹ H-NMR (DMSO-d6): [ppm] = 8.41 (d, 1H, ³ J _HH 8.4 Hz, H6), 8.31 (s, 1H, H6 ′), 7.94 (br, dd, 1H, ³ J _HH = 8.4 Hz, ³ J _HH = 6.8 Hz, H5), 7.54 (d, 1 H, ³ J _HH = 5.4 Hz, H3), 7.30 (br, dd, 1H, ³ J _HH = 6.8 Hz, ³ J _HH = 5.4 Hz, H4), 7.11 (d, 1H, ³ J _HH = 8.0 Hz, H4 ′), 6.74 (d, 1H, ³ J _HH = 8.0 Hz, H3 ′).
¹³ C { ¹ H} NMR (DMSO-d6): [ppm] = 168.5 (q), 163.0 (q), 147.3 (t), 145.6 (q), 138.3 (t ), 136.7 (t), 131.7 (t), 127.3 (t), 124.6 (t), 120.5 (t), 120.4 (q), 102.8 (q) .

fac-tris [2- (2-pyridinyl-κN) (4-fluoro-5-cyanophenyl) -κC] iridium (III))
Method A: Use of Cyanating Agent 1 In 200 ml of NMP, 9.455 g (10 mmol) of fac-tris [2- (2-pyridinyl-κN) (4-fluoro-5-bromophenyl) -κC] iridium (III) A suspension containing 5.374 g (60 mmol) of copper (I) cyanide was heated at 160 ° C. for 60 hours. See Example 1, Method A for preparation. The yield was 7.638-7.710 g corresponding to 97.5-98.4% with a purity of> 99.0% by ¹ H-NMR.
¹ HNMR (DMSO-d6): [ppm] = 8.46 (d, 1H, ⁴ J _HF = 6.4 Hz, H6 ′), 8.40 (br, d, 1H, ³ J _HH = 8.3 Hz, H6), 8.01 (br, dd, 1H, ³ J _HH = 8.3 Hz, ³ J _HH = 7.5 Hz, H5), 7.48 (br, d, 1H, ³ J _HH = 5.6 Hz, H3), 7.33 (br, dd, 1H, ³ J _HH = 7.5 Hz, ³ J _HH = 5.6 Hz, H4), 6.37 (d, 1 H, ³ J _HF = 10.05 Hz, H3 ' ).

fac-tris [2- (2-pyridinyl-κN) (4,6-difluoro-5-cyanophenyl) -κC] iridium (III)
Method A: Use of Cyanating Agent 1 9.635 g (10 mmol) of fac-tris [2- (2-pyridinyl-κN) (4,6-difluoro-5-bromophenyl) -κC] iridium (III) in 200 ml of NMP ) And 5.374 g (60 mmol) of copper (I) cyanide were heated at 160 ° C. for 60 hours. See Example 1, Method A for preparation.
The yield was 7.638-7.710 g corresponding to 97.5-98.4% with a purity of> 99.0% by ¹ H-NMR.
¹ H-NMR (DMSO-d6): [ppm] = 8.46 (br, d, 1H, ³ J _HH = 8.2 Hz, H6), 8, 21 (br, dd, 1H, ³ J _HH = 8 .2 Hz, ³ J _HH = 7.0 Hz, H5), 7.47 (br, d, 1 H, ³ J _HH = 5.8 Hz, H3), 7.30 (br, dd, 1 H, ³ J _HH = 7 0.0 Hz, ³ J _HH = 5.8 Hz, H4), 6.32 (dd, 1 H, ³ J _HF = 10.05 Hz, ⁵ J _HF = 1.35 Hz, H3 ′).

fac-tris [2- (2-pyridinyl-κN) (4-methoxy-5-cyanophenyl) -κC] iridium (III)
Method A: Use of cyanating agent 1 In 200 ml of NMP, fac-tris [2 (2-pyridinyl-κN) (4-methoxy-5-bromophenyl) -κC] iridium (III) 9.816 g (10 mmol) and cyanide A suspension containing 5.374 g (60 mmol) of copper (I) chloride was heated at 145 ° C. for 60 hours. See Example 1, Method A for preparation. The yield was 7.935-8.030 g, corresponding to 96.7-97.9%, with a purity of> 99.0% by ¹ H-NMR.
¹ H-NMR (DMSO-d6): [ppm] = 8.27 (d, 1H, ³ J _HH = 8.4 Hz, H6), 8.21 (s, 1H, H6 ′), 7.94 (br , Dd, 1H, ³ J _HH = 8.4 Hz, ³ J _HH = 6.7 Hz, H5), 7.54 (d, 1 H, ³ J _HH = 5.1 Hz, H3), 7.30 (br, dd _{^{; 1H, 3 J HH = 6.7Hz}} , 3 J HH = 5.1Hz, H4), 6.41 (s, 1H, H3), 3.48 (s, 3H, CH 3).

2. Production and characterization of organic electroluminescent element-containing compounds according to the present invention.
The LED was produced by the general method outlined below. Of course, this had to be adapted to the situation given in each case (for example layer thickness variations to achieve optimum efficiency and color).

General method for production of OLED:
After the ITO coated substrate (eg glass substrate, PET film) is cut to the correct size, it is washed in an ultrasonic bath (eg soap solution, millipore water, isopropanol) in several washing steps. . For the purpose of drying them N ₂ - blowing pistol, placed in a desiccator. Prior to vapor deposition with organic layers, they are treated with an ozone-plasma apparatus for about 20 minutes. It is recommended to use a polymer hole injection layer as the first organic layer. Typically this is a conjugated conducting polymer such as, for example, polyaniline derivatives (PANI) or polythiophene derivatives (eg PEDOT, BAYTRONP ™ from Bayer). This is deposited by spin coating.

  The organic layer is sequentially deposited by vapor deposition in a high vacuum facility. The thickness of each layer and the deposition rate are monitored and adjusted by a quartz resonator. As mentioned above, the individual layers can also consist of one or more compounds, i.e. in principle a host material doped with a guest material, which is achieved by co-evaporation from two or more sources. The

  An electrode is also deposited on the organic layer. Typically this occurs by thermal evaporation (Balzer BA360 or Pfeiffer PLS500). Subsequently, a transparent ITO electrode as an anode and a metal electrode (for example, Ca, Yb, Ba—Al) as a cathode are brought into contact with each other to determine device parameters.

Similar to the general method described above, a blue-emitting OLED with the following structure was produced:
PEDOT 20 nm (spun on from water; PEDOT obtained from Bayer; poly [3,4-ethylenedioxy-2,5-thiophene]
MTDATA 20 nm (deposited; MTDATA obtained from SynTec; 4, 4 ′, 4 ″ -tris (3-methylphenyl-phenylamino) triphenylamine)
S-TAD 20 nm (deposited; S-TAD was obtained according to WO 99/12888; 2,2 ′, 7,7′-tetrakis (diphenylamino) -spirobifluorene)
CPB 20 nm (deposited; CPB was obtained from Aldrich, further purified and finally sublimed twice; 6% triplet emitter fac-tris [2- (2-pyridinyl-κN) (4-fluoro- 5-Cyanophenyl) -κC] -iridium (III) doped 4,4′-bis- (N-carbazolyl) biphenyl) (compare with Example 3)
BCP 8 nm (deposited; BCP was obtained from ABCR and used as received; 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)
AIQ ₃ 20 nm (deposited: AIQ ₃ was obtained from Shintech; Tris (quinoxalinato) aluminum (III)
150 nm as Yb cathode.

These non-optimized OLEDs were evaluated as standards; the EL spectrum is shown in FIG. Aside from color, a very great advantage of these OLEDs is the flatness of the efficiency curve, which means that very high efficiencies are achieved even for very high luminosity (eg 10000 Cd / m ² ). is doing. This is particularly important for use in simple matrix driven displays.

It is a figure which shows the characteristic data of OLED by Example 1. FIG. 6 is a diagram showing characteristic data of an OLED according to Example 3. FIG.

Claims (14)

A compound comprising the following chemical formula (I) or a compound comprising the chemical formula (II).

(In the formula, symbols and subscripts have the following meanings:
M Rh, Ir;
Z is N, CR, all the same or different;
YO, S, Se;
R is _{H, F, Cl, NO 2} , CN, a 1-20 linear or branched or cyclic having carbon atoms, an alkyl group or an alkoxyl group,
here,
One or more non-neighboring CH ₂ groups in the alkyl group or alkoxyl group can be replaced with —O—, —S—, —NR ¹ —, or —CONR ² —,
Also here
One or more H atoms in the alkyl or alkoxyl group can be substituted with F, or an aryl or heteroaryl group having 4 to 14 carbon atoms;
The aryl group or heteroaryl group having 4 to 14 carbon atoms is
One or more _F, Cl, NO 2, CN, linear or branched or cyclic having 1 to 20 carbon atoms may have an alkyl group or an alkoxyl group as a substituent,
Several of the substituents R in here, in the same ring, and in which the combined two different rings, may be further formed another monocyclic system or polycyclic system;
R ¹ and R ² are the same or different and are H or an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms;
n is 1, 2 or 3) A compound comprising the following chemical formula (Ia) or a compound comprising (IIa).

(In the formula, symbols and subscripts have the same meaning as in claim 1) A compound consisting of the following chemical formula (III) or a compound consisting of (IV).

(In the formula, symbols M, Y, R, and subscript n have the same meaning as in claim 1;
a is 0, 1, 2, 3 or 4;
b is 0, 1, 2 or 3) A compound consisting of the following chemical formula (IIIa) or a compound consisting of (IVa).

(In the formula, symbols and subscripts have the same meaning as in claims 1 and 3) A compound comprising the chemical formula (I) or a compound comprising the chemical formula (II) is obtained by a conversion reaction of the compound comprising the chemical formula (V) or the compound comprising the (VI) with a cyanating agent. A method for producing the compound according to 1.

(Wherein X is Cl, Br or I, where M and the Z, Y groups, subscript n have the same meaning as in claim 1) A compound consisting of the chemical formula (III) or a compound consisting of the chemical formula (IV) is obtained by a conversion reaction of a compound consisting of the following chemical formula (VII) or a compound consisting of (VIII) with a cyanating agent. 3. A method for producing the compound according to 3.

Wherein X is Cl, Br or I, wherein the radicals and subscripts Y, R, a and b have the same meaning as in claims 1 and 3.   7. The method according to claim 5, wherein a reagent having a cyanide source containing cyanide ions in an ion-bonded or coordinate-bonded form is used as the cyanating agent.   The method according to any one of claims 5 to 7, wherein copper (I) cyanide or nickel (II) cyanide is used as the cyanating agent (1).   As the cyanating agent (2), zinc (II) cyanide in the presence of zinc and zinc or nickel (II) in the presence of nickel or palladium or nickel or palladium compounds and optionally phosphorus-containing additives The method according to any one of claims 5 to 7, wherein: The molar ratio of the cyanating agent (1) or (2) to the compound of formula (V), the compound of formula (VI), the compound of formula (VII), or the compound of formula (VIII) is 1 10. A method according to claim 8 or 9 , characterized in that the ratio is from 1 to 10: 1. 11. The method according to claim 9 , wherein the cyanating agent (2) has a molar ratio of zinc (II) cyanide to zinc of 1: 0.1 to 1: 0.001. In the cyanating agent (2), the molar ratio of nickel, nickel compound, palladium or palladium compound to the compound of formula (V) (VI) (VII) or (VIII) is 0.1: 1 to 0.00001: The method according to claim 9 , wherein the method is one. In cyanide agent (2), phosphorus-containing additive to nickel, a nickel compound, the molar ratio of palladium or palladium compound is 0.5: 1 to 1000: according to claim 9 ～10,12 characterized by comprising a 1 The method of any one of Claims.   Organic light-emitting diodes (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs) containing at least one compound according to any one of claims 1 to 4. ), Organic solar cells (O-SCs), or organic laser diodes (O-lasers).

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